Hydrocarbon oil composition



United States Patent 3,017,357 HYDROCARBON OIL COMPOSITION Henryk A.Cyba, Chicago, Ill., assignor, by mesne assignments, to Universal OilProducts Company, Des Plaines, Ill., a corporation of Delaware NoDrawing. Filed May 12, 1958, Ser. No. 734,408 6 Claims. (Cl. 252-325)This invention relates to a novel additive for hydrocarbon oil and moreparticularly to a novel method of improving hydrocarbon oil in a numberof important properties.

During processing, transportation, storage and/or use, hydrocarbon oilsgenerally deteriorate, particularly when subjected to elevatedtemperature. For example, hydrocarbon oil :being subjected tofractionation or conversion is first heated to an elevated temperature.Such heating may be effected in an externally fired furnace or it may beaccomplished by heat exchange with a hotter fluid. In the first case,the hydrocarbon fluid is passed through tubes during such heating and,in many cases, deposit formation occurs in the tubes and results in lossof efficient heating and/or plugging of the furnace tubes. In heatexchange systems the hydrocarbon oil is passed either through tubesdisposed in a shell or through the shell surrounding the tubes. Duringheating of the oil, deposit formation occurs either within the tubes orin the hotter sections of the shell, with the result of decreasedefficiency in heat transfer and even in plugging of the tubes. Anotherexample in which hydrocarbon oil is passed in heat exchange is in thecase of jet fuel, where the jet fuel is passed in heat exchange with thehot exhaust gases, both to cool the exhaust gases and to heat theincoming fuel. Temperatures as high as 500 F. or more are encounteredfor at least short periods of time, with the result that depositformation occurs and either plugs the heat exchanger or interferes withefficient heat transfer.

Other examples where instability of the hydrocarbon oil is a problem arehydrocarbon oils heavier than gasoline including diesel oil, heateroils, burner oils, range oils, fuel oils, transformer oils, hydraulicoils, slushing oils, etc. Deposit formation in these oils isobjectionable because it results in plugging of filters, strainers,burner tips, injectors, etc., reduction in viscosity and accordingly inflowing properties, as Well as the formation of varnish and sludge inthe diesel engine. In addition to preventing these objectionable depositformations, the novel additive of the present invention also functionsto retard corrosion of metal surfaces in contact with hydrocarbon oiland water. It is well known that wtaer generally is present inhydrocarbon oils and results in corrosion of piping, pumps, shells,fractionators, receivers, storage tanks, etc., as well as internalequipment such as bafile plates, bubble trays, bubble caps, etc.

In addition to serving the important functions hereinbefore set forth,the novel additive of the present invention also serves to lower thepour point of the hydrocarbon oil. This is of advantage in the case ofheavier oils which are being pumped and also of particular advantage inthe case of lubricating oils, gas turbine oils, steam turbine oils, jetturbine oils, marine oils, etc. in order that the oil retain its flowingproperties at lower temperatures. In addition to reducing pour point andlowering the cold test, the additive also improves the viscosity indexof lubricating oil.

The additive of the present invention also serves an important functionin the case of gasoline or naphtha. As hereinbefore set forth, theadditive serves "as a cor rosion inhibitor and therefore reducescorrosion problems in storage tanks, pipe lines, etc., as well as in thecarburetor, fuel lines, etc., used in conjunction with internalcombustion engines.

From the above description, it will be noted that the novel additive ofthe present invention serves to improve hydrocarbon oil in a number ofdifferent ways. The hydrocarbon oil includes gasoline, naphtha, jetfuel, kerosene, burner oil, heater oil, range oil, gas oil, fuel oil,lubricating oil, residual oil, etc. As hereinbefore set forth, theadditive may be incorporated in the oil prior to heating for furtherprocessing, or it may be incorporated in the oil after such treatment.

In one embodiment the present invention relates to a method of improvinga hydrocarbon oil which comprises incorporating therein a stabilizingconcentration of an alkyl acid phosphate salt of the reaction product ofan epihalohydrin compound with an amine compound having at least 12carbon atoms.

In a specific embodiment the present invention relates to a method ofpreventing deposit formation in a heat exchanger through which twofluids at different tempera tures are passed which comprisesincorporating in at least one of said fluids, in an amount sufficient toprevent deposit formation, a mixture of monoand dioctyl acidorthophosphate salts of the reaction product of epichlorohydrin withhydrogenated tallow amine.

In still another embodiment the present invention relates to a method ofimproving burner oil which comprises incorporating therein a stabilizingconcentration of a mixture of the monoand di-tridecyl acid phosphatesalts of the reaction product of epichlorohydrin and tallow amine.

In still another embodiment the present invention relates to hydrocarbonoil containing a stabilizing concentration of the novel additive hereinset forth.

The novel additives of the present invention also are new compositionsof matter and are being so claimed in the present application.

As hereinbefore set forth, the novel additive of the present inventionis an alkyl acid phosphate salt of the reaction product of anepihalohydrin compound with an amine compound having at least 12 carbonatoms. It is essential in the present invention that the amine compoundused in preparing the reaction product contains at least 12 carbon atomsand preferably at least 15 carbon atoms. Generally the total number ofcarbon atoms in the amine will not exceed about 40 carbon molecule.tains a straight chain of at least 3 carbon atoms attached to thenitrogen atom. In this preferred embodiment, the alkyl group attached tothe nitrogen atom is of normal configuration and not secondary, tertiaryor of cyclic configuration. However, the alkyl group may containbranching in the chain, provided such branching occurs on the fourthcarbon atom from the nitrogen atom or further distant therefrom.

Any suitable alkyl amine meeting the requirements set forth herein maybe used in preparing the additive of the present invention. In additionto the above requirements, it is essential that the alkyl amine is aprimary or secondary amine; that is, only one or two of the hydrogenatoms attached to the nitrogen atom are substituted by alkyl groups.Tertiary amines (no hydrogen atom attached to the nitrogen atom) cannotbe used in the present invention. It is understood that the term alkylamine is used in the present specifications and claims to includeprimary alkyl amines, secondary alkyl amines, polyamines, N-alkylpolyamines, N,N'-dia1kyl polyamines, etc., all of which meet therequirements hereinbefore set forth.

Illustrative examples of primary alkyl amines include dodecyl amine,tridecyl amine, tetradecyl amine, pentaatoms per. In a preferredembodiment the amine con-.

decyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine,nonadecyl amine, eicosyl amine, heneicosyl amine, docosyl amine,tricosyl amine, tetracosyl amine, pentacosyl amine, hexacosyl amine,heptacosyl amine, octacosyl amine, nonacosyl amine, triacontyl amine,hentriacontyl amine, dotriacontyl amine, tritriacontyl amine,tetratriacontyl amine, pentatriacontyl amine, hexatriacontyl amine,heptatriacontyl amine, octatriacontyl amine, nonatriacontyl amine,tetracontyl amine, etc. Conveniently the long chain amines are preparedfrom fatty acids or more particularly from mixtures of fatty acidsformed as products or by-products. Such mixtures are availablecommercially, generally at lower prices and, as another advantage of thepresent invention, the mixtures may be used without the necessity ofseparating individual amines in pure state.

An example of such a mixture is hydrogenated tallow amine which isavailable under various trade names including Alamine H26D and ArmeenHTD. These products comprise mixtures predominating in alkyl aminescontaining 16 to 18 carbon atoms per alkyl group, although they containa small amount of alkyl groups having 14 carbon atoms, and also meet theother requirements hereinbefore set forth.

Illustrative examples of secondary amines include di- (dodecyl) amine,di-(tridecyl) amine, di-(tetradecyl) amine, di(pentadecyl) amine,di-(hexadecyl) amine, di- (heptadecyl) amine, di-(octadecyl) amine,di-(nonadecyl) amine, di-(eicosyl) amine, etc. In another embodiment,which is not necessarily equivalent, the secondary amine will containone alkyl group having at least 12 carbon atoms and another alkyl grouphaving less than 12 carbon atoms, both of the alkyl groups having astraight chain of at least 3 carbon atoms attached to the nitrogen atom.Illustrative examples of such compounds include N-propyl-dodecyl amine,N-butyl-dodecyl amine, N-amyl-dodecyl amine, N-butyl-tridecyl amine,N-amyl-tridecyl amine, etc. Here again, mixtures of secondary amines areavailable commercially, usually at a lower price, and such mixtures maybe used in accordance with the present invention, provided that theamines meet the requirements hereinbefore set forth. An example of sucha mixture available commercially is Armeen ZHT which consists primarilyof dioctadecyl amine and dihexadecyl amine.

Preferred examples of N-alkyl polyamines compriseN-alkyl-1,3-diaminopropanes in which the alkyl group contains at least12 carbon atoms. Illustrative examples includeN-dodecyl-l,3-diaminopropane, N-tridecyl- 1',3-diaminopropane,N-tetradecyl-1,3-diaminopropane, N- pentadecyl-1,3-diaminopropane, Nl1exadecyl-l,3-diarninopropane, N-heptadecyl-1,3-diaminopropane,N-octadecyl-l,3diaminopropane, N-nonadecyl-1,3 diaminopropane,N-eicosyl-Lit-diaminopropane, N-heneicosyl-1,3-diaminopropane,N-docosyl-1,3-diaminopropane, N-tricosyl-1,3-diaminopropane,N-tetracosyl-1,3-diaminopropane, N-pentacosyl-1,3-diaminopropane, Nhexacosyl-l,3-diaminopropane, N-heptacosyl-l,3-diaminopropane,N-octacosyl-l,3-diaminopropane, N-nonacosyl-l,3 diaminopropane,N-triacontyl-1,3-diaminopropane, N-hentriacontyl- 1,3-diaminopropane,N-dotriacontyl-l,3-diaminopropane, N-tritriacontyl-l,3-diaminopropane,N-tetratriacontyl-1,3- diaminopropane, N-pentatriacontyl-l,3diaminopropane, N-hexatriacontyl-1,3-diaminopropane, N heptatriacontyl-1,3-diaminopropane, N octatriacontyl-l,3 diaminopropane,N-nonatriacontyl-l,3-diaminopropane, N-tetracontyl-1,3-diaminopropane,etc. As before, mixtures are available commercially, usually at lowerprices, of suitable compounds in this class and advantageously are used.for the purposes of the present invention. One such mixture is Duomeen Twhich is N-tallow-1,3- diaminopropane and predominates in alkyl groupscontaining 16 to 18 carbon atoms each, although the mixture contains asmall amount of alkyl groups containing 14 carbon atoms each. Anothermixture available 'commercially is N-coco-1,3-diaminopropane whichcontains alkyl groups predominating in 12 to 14 carbon atoms each. Stillanother example is N-soya-1,3-diaminopropane which predominates in alkylgroups containing 18 carbon atoms per group, although it contains asmall amount of alkyl groups having 16 carbon atoms.

While the N-alkyl-1,3-diaminopropancs are preferred compounds of thisclass, it is understood that suitable N-alkyl ethylene diamines,N-alkyl-l,3-diaminobutanes, N-alkyl-l,4-diaminobutanes,N-alkyl-1,3-diaminopentanes, N-alkyl-l,4-diaminopentanes, N alkyl 1,5diaminopentanes, N-alkyl-1,3-diaminohexanes, N-alkyl-l,4-diaminohexanes,N-alkyl-l,S-diaminohexanes, N-alkyl-l,6-diaminohexanes, etc., may beemployed but not necessarily with equivalent results. Also, it isunderstood that polyamines containing 3 or more nitrogen atoms may beemployed provided they meet the requirements hereinbefore set forth.Illustrative examples of such compounds include N-dodecyl-diethylenetriamine, N-tridecyl-diethylene triamine, N-tetradecyl-diethylenetriamine, etc., N- dodecyl-dipropylene triamine, N-tridecyl-dipropylenetriamine, N-tetradecyl-dipropylene triamine, etc., N-dodecyl-dibutylenetriamine, N-tridecyl-dibutylene triamine, N-tetradecyl-dibutylenetriamine, etc., N-dodecyl-triethylene tetramine, N-tridecyl-triethylenetetramine, N-tetradecyl-triethylene tetramine, etc.,N-dodecyl-tripropylene tetramine, N-trldecyl-tripropylene tetramine,N-tetradecyl-tripropylene tetramine, etc., N-dodecyl-tributylenetetramine, N-tridecyl-tributylene tetramine, N-tetradecyl-tributylenetetramine, etc., N-dodecyl-tetraethylene pentamine,N-tridecyl-tetraethylene pentamine, N-tetradecyltetraethylene pentamine,etc., N-dodecyl-tetrapropylene pentamine, N-tridecyl-tetrapropylenepentamine, N-tetradecyl-tetrapropylene pentamine, etc.,N-dodecyl-tetrabutylene pentamine, N-tridecyl-tetrabutylene pentamine,N- tetradecyl-tetrabutylene pentamine, etc.

In another embodiment, polyaminoalkanes meeting the requirementshereinbefore set forth may be employed but generally such materials arenot available commercially and, therefore, generally are not preferred.Illustrative examples of such compounds include 1,12-diaminododecane,l,l3-diaminotridecane, 1,14-diaminotetradecane, etc.

In general, it is preferred that the amine compound is a saturatedcompound and does not contain double bonds in the chain. However, insome cases, unsaturated compounds may be employed, provided they meetthe other requirements hereinbefore set forth, although not necessarilywith equivalent results. Such amine compounds may be prepared fromunsaturated fatty acids and, therefore, may be available commercially atlower cost. Illustrative examples of such amine compounds includedodecylenic amine, diododecylenic amine, N-dodecylenic ethylene diamine,N-dodecylenic-l,3-diaminopropane, oleic amine, dioleic amine, N-oleicethylene diamine, N-oleic- 1,3-diaminopropane, linoleic amine,dilinoleic amine, N- linoleic ethylene diamine,N-linoleic-l,3-diaminopropane, etc. It is understood that these aminecompounds are included in the present specifications and claims byreference to amine or amine compounds.

In another embodiment of the invention, two ditfcrent amines may bereacted with the epihalohydrin compound. At least one of the amines mustmeet the qualifications hereinbefore set forth. The other amine maycomprise any suitable compound containing primary and/or secondary aminegroups. Preferred compounds comprise ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, etc., similarpropylene and polypropylene polyamines, butylene and polybutylenepolyamines, etc. In still another embodiment, other suitablenitrogen-containing compounds may be used as, for example, urea,monoethanol amine, etc.

As hereinbefore set forth, the amine compound is reacted with anepihalohydrin compound. Epichlorohydrin is preferred. Otherepichlorohydrin compounds include 1,2-epi-4-chlorobutane,2,3-epi-4-chlorobutane, 1,2-epi-- chloropentane,2,3-epi-5-chloropentane, etc. In general, the chloro derivatives arepreferred, although it is understood that the corresponding bromo andiodo compounds may be employed. In some cases epidihalohydrin compoundsmay be utilized. It is understood that the dilfe.- ent epihalohydrincompounds are not necessarily equivalent in the same or differentsubstrate and that, as hereinbefore set forth, epichlorohydrin ispreferred.

In general, 1 or 2 mols of amine compound are reacted with 1 or 2 molsof epihalohydrin compound. It is understood that, in some cases, anexcess of amine or of epihalohydrin may be supplied to the reaction zonein order to insure complete reaction, the excess being removedsubsequently in any suitable manner. When 2 mols of amine are reactedper mol of epihalohydrin compound, the amine may comprise the same ordifierent amine compound.

In a preferred embodiment of the invention, the reaction of 1 mol ofamine compound with 1 mol of epihalohydrin compound proceeds to theformation of polymeric reaction product. In this embodiment of theinvention, the reaction is first effected at a temperature within therange hereinafter set forth, with only a portion of the reactants beingpresent in the reaction mixture. After the initial reaction iscompleted, the remaining reactants are supplied to the reaction mixtureand the reaction is completed at a higher temperature but within thesame range set forth herein. For example, a portion of the amine may befirst reacted with the epihalohydrin and then the remaining portion ofthe amine is reacted. These polymers may contain from about 3 to about20 or more recurring units and preferably from about 5 to aboutrecurring units.

The desired quantity of alkyl amine and epihalohydrin compounds may besupplied to the reaction zone and therein reacted, although generally itis preferred to supply one reactant to the reaction zone and thenintroduce the other reactant step-wise. Thus, usually it is preferred tosupply the amine to the reaction zone and to add the epihalohydrincompound step-wise, with stirring. When it is desired to react twodifferent alkyl amines with the epihalohydrin compound, theepihalohydrin compound is supplied to the reaction zone. One of theamines is added gradually, and the reaction completed, followed by theaddition of the second alkyl amine. Generally, it is preferred toutilize a solvent and, in the preferred embodiment, a solution of theamine in a solvent and a separate solution of the epihalohydrin compoundin a solvent are prepared, and these solutions then are commingled inthe manner hereinbefore set forth. Any suitable solvent may be employed,a particularly suitable solvent comprising an alcohol including ethanol,propanol, butanol, etc., Z-propanol being particularly desirable.

The reaction is effected at any suitable temperature, which generallywill be within the range of from 20 to about 100 C. and preferably iswithin the range of from about 50 to about 75 C. A higher temperaturerange of from about 30 to about 150 C. or more, and preferably of fromabout 50 C. to about 100 C., is specified when the reaction is effectedat superatmospheric pressure to increase the reaction velocity.Conveniently, this reaction is effected by heating the amine solution indilute alcohol at refluxing conditions, with stirring, gradually addingthe epihalohydrin compound thereto, and continuing the heating until thereaction is completed.

Either before or after removal of the reaction product from the reactionzone, the product is treated to remove halogen, generally in the form ofan inorganic halide salt as, for example, the hydrogen halide salt. Thismay be effected in any suitable manner and generally is accomplished byreacting the product with a strong inorganic base such as sodiumhydroxide, potassium hydroxide, etc., to form the corresponding metalhalide. The

6 reaction to form the metal halide generally is effected under the sameconditions as hereinbefore set forth. After this reaction is completed,the metal halide is removed in any suitable manner, including filtering,centrifugal separation, etc. It is understood that the reaction productalso is heated sufficiently to remove alcohol and water and this may beeffected either before or after the treatment to remove the inorganichalide.

In still another embodiment, after the reaction product of an alkylamine and epihalohydrin is prepared, the reaction product may be reactedwith other nitrogencontaining compounds including, for example, alkanolamines, urea, etc., instead of with the same or different alkyl amine ashereinbefore described. Illustrative alkanol amines include ethanolamine, propanol amine, butanol amine, pentanol amine, hexanol amine,etc.

As hereinbefore set forth, the alkyl acid phosphate of the reactionproduct prepared in the above manner is used as an additive tohydrocarbon oils. The term alkyl acid phosphate includes both the alkylacid orthophosphates and the alkyl acid pyropho-sphates. In the alkylacid orthophosphates, the monoalkyl ester, dialkyl ester or a mixturethereof may be employed. In the alkyl acid pyrophosphates, the monoalkylester, dialkyl ester, trialkyl ester or mixtures thereof may beemployed, the dialkyl ester being preferred and the ester groups may beattached to the same or different phosphorus atoms. Generally, however,this compound will be symmetrical and, thus, the alkyl ester groups willbe attached to different phosphorus atoms.

In general, at least one of the alkyl groups constituting the estercontains at least 6 and preferably at least 8 carbon atoms. Illustrativealkyl acid orthophosphates are set forth below, although it isunderstood that these are presented as preferred examples and that othersuitable alkyl acid phosphates may be employed. The preferred alkyl acidorthophosphates include monooctyl acid orthophosphate, dioctyl acidorthophosphate, mixture of monoand dioctyl acid orthophosphates,monononyl acid orthophosphate, dinonyl acid orthophosphate, mixture ofmonoand dinonyl acid orthophosphates, monodecyl acid orthophosphate,dideeyl acid orthophosphate, mixture of mono and dideeyl acidorthophosphates, monoundecyl acid orthophosphate, diundecyl acidorthophosphate, mixture of mono and diundecyl acid orthophosphates,monododecyl acid orthophosphate, didodecyl acid orthophosphate, mixtureof monoand didodecyl acid orthophosphates, monotridecyl acidorthophosphate, ditridecyl acid orthophosphate, mixture of monoandditridecyl acid orthophosphates, monotetradecyl acid orthophosphate,ditetradecyl acid orthophosphate, mixture of monoand ditetradecyl acidorthophosphates, monopentadecyl acid orthophosphate, dipentadecyl acidorthophosphates, mixture of monoand dipentadecyl acid orthophosphates,etc.

Preferred alkyl acid pyrophosphates include monooctyl acidpyrophosphate, dioctyl acid pyrophosphate, mixture of monoand dioctylacid pyrophosphates, monononyl acid pyrophosphate, dinonyl acidpyrophosphate, mixture of monoand dinonyl acid pyrophosphates, monodecylacid pyrophosphate, dideeyl acid pyrophosphate, mixture of monoanddideeyl acid pyrophosphates, monoundecyl acid pyrophosphate, diundecylacid pyrophosphate, mixture of monoand diundecyl acid pyrophosphates,monododecyl acid pyrophosphate, didodecyl acid pyrophosphate, mixture ofmonoand didodecyl acid pyrophosphates, monotridecyl acid pyrophosphate,ditridecyl acid pyrophosphate, mixture of monoand ditridecyl acidpyrophosphates, monotetradecyl acid pyrophosphate, ditetradecyl acidpyrophosphate, mixture of monoand ditetradecyl acid pyrophosphates,monopentadecyl acid pyrophosphate, dipentadecyl acid pyrophosphate,mixture of monoand dipentadecyl acid pyrophosphates, etc.

Conveniently, alkyl groups containing more than 8 carbon atoms areintroduced through the use of fatty alcohols and thus the alkyl radicalmay be selected from capryl, lauryl, myr'istyl, palmityl, stearyl,ceryl, etc. Illustrative phosphates in this class include stearyl caprylacid orthophosphate, distearyl acid orthophosphate, dicapryl acidorthophosphate, etc. In other examples, one of the alkyl groups containsless than 8 carbon atoms while the second alkyl group contains more than8 carbon atoms, and such examples are illustrated by ethyl lauryl acidorthophosphate, ethyl stearyl acid orthophosphate, ethylbutyl laurylacid orthophosphate, ethylbutyl capryl acid orthophosphate, ethylbutylstearyl acid orthophosphate, etc.

Alkyl acid phosphates including both the ortho and pyrophosphates alsoare manufactured commercially as a mixture of monoand dialkyl acidphosphates and are available at lower costs. In many cases, suchmixtures are suitable for use in preparing the salt of the presentinvention and such use, therefore, is preferred for economic reasons.

The alkyl acid phosphate salt of the reaction product of epichlorohydrinand amine compound is prepared utilizing at least 1 mol of alkyl acidphosphate per mol of the reaction product and will range up to 1 mol ofphosphate per each mol equivalent of basic nitrogen in the reactionproduct. In general, this will comprise from 1 to about 20 mols ofphosphate per 1 mol of reaction product. For example, as hereinbeforeset forth, the polymer formed by the reaction of 1 mol ofepichlorohydrin with 1 mol of amine compound will contain from about 5to recurring units, each unit containing a basic nitrogen. Accordingly,from 5 to 10 mols of phosphate are used in order to obtain the desiredsalt. It is understood that, when the polymer contains more than 10basic nitrogens, a corresponding larger number of mols of phosphatepreferably is used. Thus, in the preferred salt of the presentinvention, an equivalent mol of phosphate is used per mol of basicnitrogen, although in some cases, an excess or a deficiency of phosphatemay be used.

The salt may be prepared in any suitable manner and, in general, isprepared by admixing the alkyl acid phosphate and the reaction productat ambient temperature, preferably with vigorous stirring. The salt isreadily prepared at room temperature, although slightly elevatedtemperatures which generally will not exceed 200 F. may be employed,when desired. Excessive temperatures must not be used in order to avoidundesired reaction which will result in the liberation of water duringformation of the salt. In fact, the reaction is slightly exothermic andin some cases it may be desirable to cool the reaction vessel. Thereaction may be effected in the presence or absence of a solvent. Whenemployed, the solvent may be used either in forming a more fluid mixtureof the reactants before mixing and/ or used during the mixing thereof.Any suitable solvent may be employed and preferably is an aromatichydrocarbon including benzene, toluene, ethylbenzene, cumene, etc., ormixtures thereof. In other cases the solvent may be selected fromalcohols, ethers, ketones, etc. In many cases it is desired to marketthe salt as a solution in a suitable solvent and conveniently the samesolvent is used during manufacture of the salt as desired in the finalproduct.

The concentration of salt to be incorporated in the hydrocarbon oil willdepend upon the particular use. For example, when utilized to preventheat exchanger deposits, the salt generally is used in a concentrationof from 1 to 1000 parts per million by weight of the hydrocarbon oil.When used for other purposes, the salt may be used in a concentration offrom about 0.0001% to about 1% or more by weight of the hydrocarbon oil.It is understood that the salt is incorporated in the hydrocarbon oil inany suitable manner and generally is effected with stirring in order toobtain intimate mixing thereof. However, when introduced in a flowingstream of oil, mixing is accomplished by turbulence normally encounteredtherein,

As hereinbefore set forth, the salt is particularly ad vantageous foruse to prevent deposit formation in heat exchangers. Such heat exchangeis utilized, for example, in a hydrotreating process in which oil issubjected to hydrogen treating in the presence of a catalyst comprisingalumina-molybdenum oxide-cobalt oxide or aluminamolybdenumsulfide-cobalt sulfide. The oil, which may comprise gasoline, kerosene,gas oil or mixtures thereof, is introduced into the process at atemperature of from about ambient to 200 F. and is passed in heatexchange with reactor effluent products being withdrawn at a temperatureof from about 500 to about 800 F. The charge is heated by such heatexchange to a temperature of from about 300 to about 600 F., then isheated in a furnace or otherwise to a temperature of from about 625 toabout 800 F. and-passed with hydrogen in contact with the catalyst. Thistreatment serves to remove impurities and to hydrogenate unsaturatescontained in the charge. Another illustration is a reforming process inwhich gasoline is contacted with hydrogen in the presence of aplatinum-containing catalyst at a temperature of from about 700 to about1000 F. and the hot effluent product from the reaction zone is passed incontact with the charge in order to cool the former and heat the latter.

An example in which oil is subjected to fractionation and the charge ispassed in heat exchange with the hot efiluent products is in a crudecolumn. In this column, crude oil is subjected to distillation at atemperature of from about 600 to about 700 F. in order to remove lightercomponents as overhead and/ or side streams. In some cases the chargefirst is passed in heat exchange with the overhead and/or side streamsfrom this column and then is passed in heat exchange with the hotterproducts withdrawn from the bottom of the crude column. In this way thecharge is progressively heated and the hotter products are cooled.

The above examples are illustrative of typical uses of heat exchange toeffect economies in the process. However, difficulty is experienced inthe heat exchange due to deposit formation, with the consequentnecessity of interrupting plant operation as hereinbefore set forth. Inaccordance with the present invention, deposit formation in heatexchanger is reduced to an extent that normal plant operation need notbe interrupted for this reason.

It is understood that the advantages of the present invention may beobtained in any suitable heat exchange equipment. In general, thisequipment comprises a series of tubes or a tube coil positioned within ashell. One of the fluids is passed through the tubes, while the otherfluid is passed through the shell. The heat exchange equipment generallyis positioned externally to a fractionator or reactor. However, in somecases, the heat exchanger takes the form of a reboiler or condenser,and. either a tube coil or a shell containing tubes is positioned Withinthe lower or upper portion of the fractionator or reactor.

When the salt of the present invention is added to a finished product,it is incorporated therein with suitable mixing, and may be used alongwith other additives to be added to the oil for specific reasons as, forexample, metal deactivator, antioxidant, synergist, cetane improver,etc. As hereinbefore set forth, the salt serves to improve the oil inmany ways including preventing deposition of sediment, preventingformation of varnish or sludge, preventing corrosion of metal surfaces,depressing pour point, preventing icing, etc. It is understood that allof these improvements are not necessarily obtained in all substrateswith the same additive. However, the different oils will be improved inone or more ways as hereinbefore set forth.

The following examples are introduced to illustrate further the noveltyand utility of the present invention by not with the intention of undulylimiting the same.

Example I The salt of this example is the mixed monoand dioctyl acidorthophosphate salt of the reaction product of epichlorohydrin andtallow amine. The reaction product was prepared by the reaction of equalmol proportions of hydrogenated tallow amine (Armeen HTD) andepichlorohydrin. It will be noted that the tallow amine is a mixture ofprimary amines predominating in 16 to 18 carbon atoms per alkyl group.The reaction was eifected by first forming a solution of 2 mols ofepichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. ofxylene and 200 cc. of 2-pr0panol. A separate solution of 2 mols orArmeen HTD was prepared in an equal volume of xylene. One mol of thelatter solution was added gradually to the epichlorohydrin solution,with stirring and heating at 55-60 C. for a period of 2.5 hours. Thenanother mol of Armeen HTD was added gradually to the reaction mixture,stirred and reacted at 80 C. for 2.5 hours. One mol of sodium hydroxidethen was added with stirring and heating at 8590 C. for 3.5 hours, afterwhich another mol of sodium hydroxide was added and the mixture stirredand reacted at 85 90 C. for one hour. Following completion of thereaction, the mixture was cooled, filtered, and the filtrate then wasdistilled to remove the alcohol. It then was distilled at 160 C. underwater pump vacuum to remove the xylene solvent. The product was a whiteto off-white, hard, brittle solid having a basic nitrogen titration of3.11 meq./g.

97.95 gms. (0.3 mol equivalent of basic nitrogen) of the reactionproduct recovered in the above manner was mixed with 54.9 gms. (0.3 mol)of mixed monoand diisooctyl acid orthophosphate with stirring. Themixing was accompanied with a rise in temperature due to the exothermicheat of reaction. The product then was cooled to room temperature andthe salt was recovered as a very viscous, amber colored oil having anindex of refraction, N of 1.4750.

The salt prepared in the above manner was evaluated as a pour pointdepressant in a commercial S.A.E. 20 Mid-Continent solvent extractedlubricating oil. The salt prepared in the above manner is readilysoluble in the lubricating oil in a concentration up to 50% by weight ormore.

This lubricating oil, without additive, had an ASTM cold test of 5 F.and an ASTM pour point of F. 1% by weight of the salt prepared in theabove manner was incorporated in a sample of the lubricating oildescribed above and this served to reduce the ASTM cold test down tobelow -30 F.

Another solution was made to contain 0.5% by weight of the reactionproduct described above in another sample of the lubricating oil, andthis served to reduce the ASTM cold test to -25 F. and accordingly theASTM pour point down to 20 F.

Furthermore, the sample of lubricating oil containing 0.5% by weight ofthe salt described above had a viscosity index of 103. In contrast, thelubricating oil without additive had a viscosity index of 98.8.

From the data in the above example, it will be noted that the additiveof the present invention served to considerably depress the pour pointof the lubricating oil and to increase the viscosity index thereof.

Example II A salt prepared in substantially the same manner as describedin Example I was evaluated in a method re, ferred to as the Erdco Test.In this method, heated oil is passed through a filter, and the timerequired to develop a diflerential pressure across the filter of 25 in.Hg is determined. It is apparent that the longer the time, the moreeffective is the additive. However, with a very effective additive, thetime to reach a differential pressure across the filter of 25 in. Hg islengthened beyond reasonable limits that the test is stopped after about300 minutes and the differential pressure at that time is reported.

The oil used in this example is a commercial J.P.-6 jet fuel. Whenevaluated for use as a jet fuel, which normally encounters highertemperature, the test is run at a higher temperature. The preheater isrun at a temperature of 400 F. and the filter is run at a temperature of500 F. The jet fuel, without additive, developed a differential pressureacross the filter of 25 in. Hg in 60 minutes. Another sample of thisfuel containing 0.005% by weight of the salt described in Example I hada zero difierential pressure after 300 minutes.

From the above data, it will be noted that the salt of the presentinvention was very efiective in preventing filter plugging, even whenevaluated at the exceptionally high temperature. Accordingly, the fuelcontaining additive is satisfactory for use as a jet fuel, whereasplugging difficulties are encountered in the absence of the additive.

Example III The salt of this example was prepared as the ethyl laurylacid orthophosphate of the reaction product of epichlorohydrin withtallow amine. Another sample of the reaction product prepared in themanner described in Example I was mixed with the phosphate in thefollowing proportions: 97.95 gms. (0.3 mol equivalent of basic nitrogen)was mixed with 93.18 gms. (0.3 mol) of ethyl lauryl acid orthophosphatewith stirring. Here again the reaction mixture increased in temperaturedue to the exothermicity of the reaction. The product was cooled and thesalt recovered as a waxy solvent having a melting range of 38-44 C.

The salt prepared in the above manner was evaluated as a pour pointdepressant in another sample of the lubricating oil described in ExampleI. 1% by weight of the salt served to reduce the ASTM cold test to -20F. and the ASTM pour point test to 15 F. When compared to the ASTM coldtest of 5 F. and pour point of 10 F., it will be noted that the salt waseffective in depressing the pour point of the oil.

Example IV The additive of this example comprises the mixed monoanddi-tridecyl acid orthophosphate salts of the reaction product preparedin the manner described in Example I. 25 gms. of the reaction productwere mixed with 9.4 gms. of mixed monoand di-tridecyl phosphate andreacted for 30 minutes at 50 C. 9.4 gms. of xylene were added to thereaction mixture to form a solution containing 50% by weight of activeingredient.

The salt prepared in the above manner was evaluated according to theCPR. fuel coker thermal stability test. In this test, the oil heated tothe specified temperature is passed through the annular spacesurrounding a heated inside tube of 17" length and /2" diameterpositioned within an outside tube of inside diameter. The inside tube isheated by means of a heating coil positioned therein to a temperature ofeither 300 or 400 F. depending upon the particular fuel being evaluated.The test is conducted for 300 minutes, at a pressure of pounds persquare inch, and a flow rate of 6 pounds of fuel per hour. Following therun the equipment is dismantled, 13" or less of the inner tube is markedoff in 1" increments and the deposits on the outside surface of theheated inner tubes are rated by visual comparison with standard metalcoupons. In general the rating is substantially as follows:

#WNHO The ratings for the individual 1" increments are added together togive a final tube rating. Military specifications 1 l for jet fuelsrequire that none of the 1" increments rates poorer than 3.

The fuel evaluated in this example is a J.P.6 commercial fuel and wastested at 400 F. A sample of the jet fuel evaluated in the above mannerhad a tube rating of 15. 25 parts per million by weight of the saltdescribed above was incorporated in another sample of this fuel and,when evaluated in the above manner, the tube rating was 6. No 1"increment rated higher than 2.

It will be noted that the reaction product of the present inventionserved to considerably reduce deposit formation.

Example V Another sample of the salt prepared as described in Example IVwas evaluated in the Erdco Test. The fuel, without additive, developed adifferential pressure of 25 in. Hg in 51 minutes. In contrast, a sampleof the fuel containing 25 parts. per millon by weight of the saltdescribed in Example IV exhibited no increase in differential pressureafter 300 minutes. Here again it will be noted that the salt of thepresent invention was very effective in retarding deposit formation.

Example VI The salt prepared in the manner described in Example IV alsowas evaluated as a corrosion inhibitor. In this evaluation, which is amodified N.I.L.I.25017 procedure, 300 cc. of depolarized isooctane, towhich 30 cc. of synthetic sea water is added, is placed in a beaker opento the atmosphere. A steel strip of thickness and A3" wide is welded toa similar strip enclosed in a glass tube. The probe then is suspended inthe mixed oil-water suspension, heated to and maintained at 100 F. for20 hours. The extent of corrosion is determined by measuring the loss inconductivity which in turn is converted to loss of steel, reported asmicro inches penetration. When a blank or control sample of theoil-water emulsion is evaluated in the above manner, the corrosion isreported as about 150 micro inches penetration. In contrast, in anotherevaluation in which 60 parts per million of the salt described inExample IV was incorporated in the oil-water suspension, no loss inconductivity and accordingly no corrosion was recorded.

Example VII The salt prepared in the manner described in Example I isused in a commercial Unifining Unit to prevent heat exchanger deposits.In this unit gasoline is subjected to hydrotreating in the presence ofan alumina-molybdenum oxide-cobalt oxide or alumina-molybdenumsulfide-cobalt sulfide catalyst. The gasoline charge is introduced at atemperature of 200 F. and is passed in heat exchange with reactorefiiuent being withdrawn at a temperature of about 675 F. This serves toheat the charge to a temperature of about 550 F. and to cool the reactoreffluent to a temperature of about 325 F. In this unit the charge ispassed through the tubes of the exchanger and the reactor effluent ispassed through the shell. 15 parts per million by weight of the salt isincorporated in the gasoline before the same is passed into theexchanger and this serves to prevent heat exchanger deposits and topermit extended use of the heat exchanger without requiring shuttingdown the plant because of the plugging of the heat exchanger tubes.

Example VIII The salt of this example is prepared as follows: Separatesolutions of epichlorohydrin and of dioctadecyl amine are prepared.One-half mol proportion of the amine solution is reacted with theepichlorohydrin solution at a temperature of 60 C. for 3 hours. Then theother half mol proportion of amine is added gradually to the reactionmixture, stirred and reacted at 75 C. for 3 hours. One mol proportion ofsodium hydroxide then is added with stirring and heating to 85 C. for 4hours. Following completion of the reaction, the mixture is cooled,filtered and recovered as a solution in xylene. To this mixture is addeddidecyl acid pyrophosphate, in a concentration of /2 mol of phosphateper each mol equivalent of basic nitrogen in the first mentionedreaction product, and the mixture is reacted at room temperature, withstirring, for 2 hours to form the salt.

Example IX The salt prepared in the manner described in Example I wasevaluated as a deicer in gasoline. This evaluation was effected in asimulated test in which ml. of a heptane fraction and 40 ml. of waterare stirred in a Waring Blendor having a polished steel beaker insertedin the top of the blender. The additive, when used, is incorporated inthe heptane fraction before being placed in the blender. The WaringBlendor is run for one minute and then 50 gms. of powdered Dry Ice isadded to the acetone, usually over a period of 10 seconds. The WaringBlendor is then run for an additional one minute. The ice deposited inthe beaker is weighed.

In a run made in the absence of an additive, 24 gms. of ice wererecovered. In another run in which 0.1% by weight of the salt describedabove was incorporated in the heptane fraction, only 11 gms. of ice wererecovered. In another run in which 0.25% by weight of the salt describedabove was incorporated in the heptane fraction, the amount of icerecovered was only 7 gms.

From these data it will be noted that the additive of the presentinvention was effective in decreasing ice formation.

I claim' as my invention:

1. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an alkyl acid phosphate salt of the reaction product of an aliphaticamine containing from 12 to about 40 carbon atoms per molecule with anepihalohydrin compound selected from the group consisting ofepichlorohydrin, 1,2-epi-4-chlorobutane, 2,3-epi- 4-chlorobutane,1,2-epi-5-chloropentane, 2,3-epi-5-chloropentane and corresponding bromoand iodo compounds, the phosphate of said salt being selected from thegroup consisting of mono-alkyl and dialkyl acid orthophosphates andpyrophosphates.

2. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an alkyl acid phosphate salt of the reaction product, formed at atemperature of from about 20 C. to about C., of from 1 to 2 mols of analkyl amine containing from 12 to about 40 carbon atoms per moleculewith from 1 to 2 mols of an epihalohydrin compound selected from thegroup consisting of epichlorohydrin, 1,2-epi-4-chlorobutane,2,3-epi-4-chlorobutane, 1,2-epi-5-chloropent'ane,2,3-epi-5-chloropentane and corresponding bromo and iodo compounds, saidsalt having been formed by first removing halogen from said reactionproduct and then reacting with the latter from 1 to 20 mols of alkylacid phosphate per mol of reaction product at from room temperature toabout 200 C., said phosphate being selected from the group consisting ofmono-alkyl and dialkyl acid orthophosphates and pyrophosphates.

3. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an octyl acid orthophosphate salt of the reaction product, formed ata temperature of from about 20 C. to about 150 C., of from 1 to 2 molsof tallow amine with from 1 to 2 mols of epichlorohydrin, said salthaving been formed by first removing chlorine from said reaction productand then reacting with the latter from 1 to 20 mols of said phosphateper mol of reaction product at from room temperature to about 200 C.

4. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof a mixture of monoand dioctyl phosphate salts of the reaction product,formed at a temperature of from about 20 C. to about 150 C. of from 1 to2 mols of hydrogenated tallow amine with from 1 to 2 moles ofepichlorohydrin, said salts having been 13 formed by first removingchlorine from said reaction product and then reacting with the latterfrom 1 to 20 mols of said phosphates per mol of reaction product at fromroom temperature to about 200 C.

5. Hydrocarbon oil containing from about 0.000l% to about 1% by weightof monoand di-tridecylacid orthophosphate salts of the reaction product,formed at a temperature of from about 20 C. to about 150 C., of from 1to 2 mols of tallow amine with from 1 to 2 mols of epichlorohydrin, saidsalts having been formed by first removing chlorine from said reactionproduct and then reacting with the latter from 1 to 20 mols of saidphosphates per mol of reaction product at from room temperature to about200 C.

6. Hydrocarbon oil containing from about 0.0001% to about 1% by weightof an octyl acid orthophosphate salt of the reaction product, formed ata temperature of from about 20 C. to about 150 C., of from 1 to 2 molsof dioctadecyl amine with from 1 to 2 mols of epichlorohydrin, said salthaving been formed by first removing chlorine from said reaction productand then reacting with the latter from 1 to 20 mols of said phosphateper mol of reaction product at from room temperature to about 200 C.

References Cited in the file of this patent UNITED STATES PATENTS

1. HYDROCARBON OIL CONTAINING FROM ABOUT 0.0001% TO ABOUT 1% BY WEIGHTOF AN ALKYL ACID PHOSPHATE SALT OF THE REACTION PRODUCT OF AN ALIPHATICAMINE CONTAINING FROM 1I TO 40 CARBON ATOMS PER MOLECULE WITH ANEPIHALOHYDRIN COMPOUND SELECTED FROM THE GROUP CONSISTING OFEPICHLOROHYDRIN, 1,2-EPI-4-CHLOROBUTANE, 2,3-EPI4-CHLOROBUTANE,1,2-EPI-5-CHLOROPENTANE, 2,3-EPI-5-CHLOROPENTANE AND CORRESPONDING BROMOAND IODO COMPOUNDS, THE PHOSPHATE OF SAID SALT BEING SELECTED FROM THEGROUP CONSISTING OF MONO-ALKYL AND DIALKYL ACID ORTHOPHOSPHATES ANDPYROPHOSPHATES.